Hydrogenation of cyclododecatriene



United States Patent 3,513,210 HYDROGENATION OF CYCLODODECATRIENELawrence Wayne Gosser, Wilmington, Del., assignor to E. I. du Pont deNemonrs and Company, Wilmington, Del., a corporation of Delaware NoDrawing. Filed Feb. 24, 1969, Ser. No. 801,841 Int. Cl. C07c /16 US. Cl.260-666 Claims ABSTRACT OF THE DISCLOSURE 1,5,9-cyclododecatriene can beselectively hydrogenated to cyclododecene by the action of hydrogen inthe presence of a homogeneous catalyst of iridium trichloride,preferably in the presence of 1 to 5 parts of stannous chloride per partof iridium trichloride, and in the presence of an inert polar organicsolvent.

BACKGROUND OF THE INVENTION This invention relates to a method of makingcyclododecene by the hydrogenation of 1,5 ,9-cyclododecatriene.

1,5,9-cyclododecatriene containing isolated double bonds can be made bythe trimerization of butadiene [G. Wilke and M. Kroner, Angew. Chem.,71, 574 (1959); H. Tokahasi and M. Yamaguchi, J. Org. Chem., 28, 1409(1963)]. The process of the present invention provides a method forpartially hydrogenating 1,5,9-cyclododecatriene to cyclododecene, whichcan be oxidized to dodecanedioic acid [Can. Pat. 775,593, US. 3,383,398,and Br. Pat. 965,510]. Dodecanedioic acid is a valuable chemical usefulfor the production of polyamide and polyester resins, surface activeagents and the like.

SUMMARY OF THE INVENTION The process of the present invention can bedefined as reacting 1,5,9-cyclododecatriene with hydrogen in thepresence of a catalytic amount of iridium trichloride, IrCl preferablyalso in the presence of from 1 to 5 parts by weight of SnCl -2H O perpart of IrCl and in the presence of an inert organic solvent, at atemperature of 25 to 150 C. and preferably 75 to 125 C. and recoveringcyclododecene from the reaction product.

DETAILED DESCRIPTION OF THE INVENTION The process of the presentinvention is a homogeneous catalytic hydrogenation process employing aniridium trichloride catalyst. Some inert polar organic solvent is highlydesirable to assist the progress of the reaction, but this need not bepresent in an amount of more than 5% to 10% by weight of the1,5,9-cyclododecatriene. Preferably the solvent will be present in anamount sufficient to form a solution containing from 1% to 95% by Weightof 1,5 ,9-cyclododecatriene.

Suitable solvents include the aliphatic, lower molecular weightsaturated alcohols, alcohol-ethers, cyclic ethers, polyoxa ethers, N,Ndialkylamides and ketones which are liquid under the conditions of thereaction; including methanol, ethanol, propanol, isopropanol, butanol,hexanol, 2 loweralkoxyethanol, and cyclohexanol; the lower alkyl ethersof ethylene glycol and lower polyethylene glycols, such as glycoldimethyl ether and diethyleneglycol dimethyl ether; tetrahydrofuran,dioxane, trioxane, dimethylformamide, acetone, methyl ethyl ketone,methyl isobutyl ketone and the like. In general it is preferred that thesolvent have from 1 to 10 carbon atoms, but it will be realized thatother alcohols and ethers can be employed.

The preferred catalysts are those in which tin chloride is present inaddition to iridium trichloride. The tin chloride assists in forming ahomogeneous solution of the iridium trichloride and in general thecatalyst obtained is highly selective. The tin chloride is generallyemployed in the form of the hydrate SnCl -2H O, which is readilyavailable. Generally, the weight ratio of SnCI 2H O/IrCl should be fromabout 1 to about 5. Larger amounts decrease the rate of hydrogenation,while smaller amounts are ineffective in suppressing the formation ofinsoluble materials during the reaction.

The catalyst should be used in an amount effective to catalyze thereaction. Loadings as low as 0.001 gm. IrCl ml. of 1,5,9-cyclododecatriene are effective, but generally concentrations ofabout 0.01 to 0.1 gm. IrCl /ml. of 1,5,9-cyclododecatriene are preferredto obtain the best selectivity.

In general, the concentration of catalyst/ml. of solution shouldlikewise not be less than 0.001 gm. IrCl /ml. of solution, andpreferably should be from 0.005 to 0.5 gm. of IrCl /ml. of solution.

With respect to the temperature, the best results are obtained in thevicinity of C. and accordingly the preferred range of temperature isfrom 75 C. to C. Satisfactory results can be attained in the range fromabout 25 C. to C. At higher temperatures by prodnets are increased,while at lower temperatures than the optimum the selectivity of thecatalyst is decreased.

Pressure is not highly critical. Atmospheric pressure can be employed orpressure of 10,000 p.s.i. or higher. Preferred conditions are from 20p.s.i.g. to 100 p.s.i.g.

The vessel in which the reaction is conducted is not critical so long asthe materials of which the vessel is made are chemically inert.Excellent results are obtained with glass vessels; or if higherpressures are used than can be obtained with all-glass equipment,glass-lined vessels can be used. Other materials can be used, such asHastelloy-C or other chemically inert materials commonly used tofabricate industrial chemical equipment.

This invention is further illustrated by the following examples whichare not, however, intended to fully de1ineate the scope of thisdiscovery.

EXAMPLES 1-24 In these examples, the conditions and the results obtainedin hydrogenating samples of 1,5,9-cyclododecatriene are given in thetable. Two techniques were employed in these runs as indicated in thetable.

(A) Reaction using a glass pressure vessel The iridium chloride andstannous chloride were placed in a 350 ml. pressure bottle of Pyrex witha magnetic stirring bar. The entire apparatus was evacuated to less than1 mm. Hg. Hydrogen was then admitted to 30 to 55 p.s.i.g. to check forleaks. The hydrogen was then vented to 0 p.s.i.g. and thecyclododecatriene and solvent were added by injection through a siliconerubber septum. Hydrogen was admitted and the mixture was stirredmagnetically until the desired amount of hydrogen was consumed. Thetimes, temperatures, and approximate pressures are given in the table.

'(B) Reaction using a vessel lined with Hastelloy-C The iridium chlorideand stannous chloride were placed in the metal reaction vessel alongwith the cyclododecatriene and solvent The closed vessel was then cooledin a Dry Ice bath and evacuated to less than 1 mm. Hg. Hydrogen was thenadmitted to an appropriate pressure. The temperature and pressure wereadjusted as indicated in the table and the vessel was shaken for thespecified time.

Product recovery and analysis With the exception of Example 22, thereaction mixture was combined with a benzene or methanol rinse of thereaction vessel. The solvents were removed with a rotary evaporator atpressures above 30 mm. Hg. The combined products were then separatedfrom nonvolatile residues by flash distillation from a distillation potat 120 C. and 0.1 to 1 mm. Hg pressure. The composition was thendetermined by VPC using a butanediol succinate column. The qualitativevalidity of these determinations was established by the use of NMR,infrared and refractive index measurements.

In the case of Example 22 using dimethyl formamide as a solvent, theproduct was added to about 75 ml. of pentane. The resulting mixture wasextracted successively with three 200 ml. portions of water, the organiclayer was dried over MgSO and the dried organic solution was thensubjected to the recovery and analytical procedures described above forthe other examples.

2. Method of claim 1 in which the inert solvent is a saturated aliphaticcompound having from 1 to 10 carbon atoms selected from alcohols andether-alcohols, cyclic ethers, polyoxa-ethers, N,N-dialkylamides andketones.

3. Method of claim 2 in which the iridium trichloride is present in anamount of from 0.01 to 0.1 gram/ml. of 1,5,9-cyc1ododecatriene.

4. Method of claim 3 in which the temperature is from 75 C. to 125 C.

5. Method of claim 4 in which the pressure is from 20 p.s.i.g. to 100p.s.i.g.

6. Method of claim 1 in which the catalyst additionally comprises from 1to 5 parts of SnCl -2H O per part of iridium trichloride.

7. Method of claim 6 in which the inert solvent is a saturated aliphaticcompound having from 1 to carbon TABLE-IRIDIUM CHLORIDE CATALYZED HYDROGENATION or 1, 5, Q-CYCLODODECATRIENE SnClz- H IlClg, 211 0 QDDTJ Milli-Time, Tcmp., pressure, Product,

Examples grams grams milliliters Solvent liters hour C. p.s.i.g. gramsna/ C.

0. 30 0.68 6.1 C2H5OH 25 1. 7 100 25 4. 3 1. 4845/25 0.30 0.68 6. 1CzHsOH 25 1. 3 100 25 4. 6 1. 4831/26 0.30 0. 68 6 CzHsOH 25 0. 5 1003050 4. 2 1. 4852/25 0.30 0 6 C2H5OH 25 1. 7 100 30 5. 3 1. 4810/26 0.300 6 02115011 25 0. 5 100 50 4. 3 1. 4800/25 0.30 0 6 0211 011 25 1. 300-05 25 4. 6 1. 4840/25 0.30 1.5 6 CzHsOH 25 6 100 50 3. 6 1. 4952/250.30 1. 5 6 CzH OH 25 6 125 130 3. 9 1. 4076/25 0.30 1. 5 6 CaHsOH 25 6125 1, 300 4. 6 1. 4012/25 0.30 0. 68 6 CQHfiOH 25 12 26-32 0, 800 4.5 1. 4068/25 0. 30 0. 68 6 0211 011 25 16 51-55 10-40 4. 8 1. 4892/25 0.30 0. 68 0 CHaOH 25 0. 5 100 34-50 5. 0 1. 4875/25 0.30 0. 68 6 n-CaHaOH25 1 100 21-45 5.2 1. 4841/25 0. 30 0.68 6 11-CaH7OH 25 1. 5 08-102 20404. 7 1. 4870/25 0. 30 0. 68 24 ll-C H OH 7 6 100 50-100 18. 8 1. 4801/250.30 0.68 n-CaH1OII 2 6 125 50-100 22. 7 1. 4072/ 0. 030 0. 068 (i C2HOH 25 12 125 50 5. 0 1. 4920/25 0. 0. b8 20 C H OH 2 6 125 2,100 24.3 1. 4020/25 0. 030 0. 068 ..4 C H OH 6 6 100 2, 000 20. 3 1. 4041/25 0.030 0. 068 [H 0 2 21 125 4. 7 1. 4021/26 0. 30 0. 68 0 CgHgOH 25 1. 7 404. 0 1. 4852/20 0.30 0. 68 6 DMF 20 1 40 3. 4 1. 4880/27 0. 30 0. 68 6THF 25 6 100 50 4. 8 1. 4860/25 0. 30 0.68 6 CHQCO CH 20 2. 5 100 40 4.0 1. 4012/27 VPC analysis NM R integra- Percent Cyclododecenes TTT-CDDItion ratio eyc1odo +dienes, CDDT, Unknown, Reaction Examples olefinH/satd H dccane Percent trans/cis percent percent percent vessel 0. 1030. 4 Glass. 0. 002 1 D 0. 133 6. 5 0. 007 12. 6 0. 0695 20. 8

0.118 95. 3 3.. 0.276 0 7 31. 4 0. 53. 5 IIastelloy-C 0. 275 25. 5 0.275 54. 6 D0. 0. 225 7. 6 44. 8 0. 710 33. 0 D0. 0.272 3. 3 22. 6 0.3040. 4 D0. 0. 184 3. 7 69. 1 0. 705 23. 1 Glass. 0. 156 1. 5 79. 4 1. 0214. 6 Hastelloy-C 0.136 1. 8 85. 4 1. 27 10. 7 ass. 0.123 2.4 81.0 0.0813.4 Do. 0. 076 19. 0 79. 0 1. 08 0. 9 Hostelloy-C 0.246 3. 0 32. 5 0.295 42. 6 l0. 0 2. 0 D0. 0.233 2. 6 56. 7 0.47 35. 1 2. 0 2. 8 Glass. 0.257 2. 0 49. 7 0. 52 37. 8 15. 1 5. 2 Hastelloy-C 0. 260 2. 5 32.8 0.5444. 8 18. 6 1. 2 Do. 0.247 5. 2 42. 0 0.45 42 7. 7 2.1 Glass. 0.128 6.270.8 1.23 11.7 0.0 1.7 Do. 0. 172 1.2 60. 4 0.92 23. 5 2.1 3. 6 Do. 0.142 5. 7 81. 2 1. 20 10.3 1.1 1. 7 Hastelloy-C 0. 232 0.3 55. 6 0.45 36.4 2.0 4. 0 lass.

1 CDDT=trans,trans,eis-1, 5, 9-cyclododeeatriene.

Z TTT-CDDT=trans,trans,trans-l,5,0-eyclod0deeatr1enc. 3DMF=dimethy1lormamide.

4 THF =tetrahydroiuran.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. Method which comprises reacting 1,5,9-cyclododecatriene with hydrogenin the presence of a catalytic amount of iridium trichloride and aninert polar organic solvent at a temperature of 25 C. to 150 C. andrecovering cyclododecene from the reaction product.

atoms selected from alcohols and ether-alcohols, cyclic ethers,polyoxa-ethers, N,N-dialkylamides and ketones.

8. Method of claim 7 in which the iridium trichloride is present in anamount of from 0.01 to 0.1 gram/ml. of 1,5,9-cyclododecatriene.

9. Method of claim 8 in which the temperature is from 75 75 C. to C.

10. Method of claim 9 in which the pressure is from 20 3,458,547p.s.i.g. to 100 p.s.i.g. 3,369,052 2,360,555

References Cited 3,022,359

UNITED STATES PATENTS 5 3,316,319

3,360,577 12/1967 Pickles. 3,408,415 10/1968 Dovell. 3,251,892 5/1966Scofelder.

DELBERT E. GANTZ, Primary Examiner V. OKEEFE, Assistant Examiner

